Application of electrochemical reactor divided by cellulosic membrane for optimized simultaneous removal of phenols,chromium, and ammonia from tannery effluents

The post treatment of simulated tannery wastewater was evaluated in an electrochemical oxidation process under galvanostatic conditions. A continuous flow reactor divided by a cellulosic membrane consisted of Ti/SnO₂–Sb anodes and iron cathodes was used. Central composite design and response surface methodology (RSM) were applied to investigate the effects of six operational parameters, namely initial concentration of total phenols (TPh), total chromium (TCr), total ammonia nitrogen (TAN), flow rate (Q), current intensity (I), and electrode surface area (A). Effectiveness of the innovative cellulosic membrane was proven by considerable pH variations in the anolyte and catholyte chambers. A faster removal rate was observed for TPh and TAN, followed by TCr. The treatment level was very sensitive to Q and I in the studied ranges. RSM showed the removal efficiencies of 78.14%, 63.42%, and 86.09% for TPh, TCr, and TAN, respectively, are achieved under optimal conditions with consumption of only 9.03 kWh m^?3 electrical energy. Chlorinated compounds such as chloroform, 2,4-dichlorophenol, and chlorobenzene were detected as the degradation intermediates. According to the obtained results, electrolysis in the divided cell with cellulosic membrane is a practical, cost-effective method for advanced treatment of tannery effluents.     

Comments on the Carcinogenicity and Mutagenicity of metals and their compounds†

The carcinogenicity of metals has received extensive study, both epidemiologically and in the laboratory. These have included case reports of occasional human occurrence or clusters of cancer cases as well as extensive epidemiologic studies; in addition, there has been significant laboratory research on the whole animals and in vitro systems. This body of information will be examined selectively.

I will not in this paper attempt a comprehensive review of the mutagenicity and carcinogenicity of metals and their compounds. Rather, I will attempt to set forth some historical perspectives, and to comment on some current gaps and needs.

Other papers in this workshop have presented thorough and very current reviews of most of the topics briefly noted in this presentation and do not require repetition here.

The cancer issue has been studied and reported on far more extensively than that relating to heritable mutations. There has been in recent years increasing interest in the use of short term tests for mutagenicity and cell transformation. These, however, are primarily with respect to their relationship to cancer production rather than to germ cell injury. Interest in cancer from metal compounds goes back a long time; in fact, one of the earliest reports was on the carcinogenicity of arsenic not many decades after the pioneering report of Sir Perceval Pott on cancer in chimney sweeps. Since then cancer has been definitely associated in humans with chromium compounds, nickel, and with less assurance but probably definitely with beryllium and cadmium. The confirmation of these findings in laboratory animals has been uneven. In the case of arsenic, for example, there has been only limited success in the production of cancer in laboratory animals with arsenic.

Many other metals have been found in laboratory studies to produce cancer, although with most of these, evidence of production of cancer in humans is either absent or extremely uncertain.

The extensive body of recent information relating to the testing of metals with a variety of short term tests will be briefly reviewed.     

The use of the embryo‐culture techniques in the research on the Teratogenic and Mutagenic properties of metals†

Actually, embryos can be cultured from the one‐cell stage up to the blastocyst stage, and their development can be easily monitored at any time: severe effects caused by toxic compounds are traduced by rapid embryonic death, less pronounced effects can be expressed by a lowered cleavage activity or by an arrest of the development from a particular stage. The system can be improved by transferring the embryos at the blastocyst stage in another more complete medium where they can “implant”; and form an inner cell mass with differentiated ectoderm and endoderm. Since last years, it has also become possible to culture postimplantation rodent embryos for short periods involving a number of particularly critical stages of organogenesis, such as the formation and closure of the anterior neuropore. Embryo‐culture also represents a useful system to study cytogenetic effects of chemicals which are often linked to lethal or teratogenic effects. These different possibilities are illustrated by examples of studies already performed with metals, and dealing with their teratogenic and/or cytogenetic effects on pre‐ and postimplantation rodents.     

Occupational exposures,delivered doses and exposure limits for chromium and nickel†

The interaction of HCH (50 mg/kg) and dietary protein levels on microsomal drug metabolizing enzymes system and liver lipids were studied in the rats for 90 days. The results indicated that rats fed a lower protein diet and HCH has a higher rate of mortality, lower rate of growth and an increased liver weight. A significant induction in the hepatic microsomal aminopyrine‐N‐demethylase, p‐nitroanisole‐O‐dealkylase, benzo(a)pyrene hydroxylase and glutathione‐S‐transferase activity was observed in pesticide treated animals as compared to control animals. The pathological changes observed in liver of HCH treated animals consisted mainly of necrosis and fatty degeneration of hepatocytes. HCH also induced the significant accumulation of cholesterol, triglycerides, phospholipid and total lipid in liver in low protein diet animals. Protein accelerates the metabolism of HCH, resulting in a decrease of HCH concentration with the increase of dietary protein level. A close correlation existed between lipid accumulation, induction of drug metabolizing enzyme system and deposition of HCH in liver.     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Preliminary Evaluation of the Use of Phosphogypsum for Reef Substrate. I. A Laboratory Study of Bioaccumulation of Radium and Six Heavy Metals in an Aquatic Food Chain

Phosphogypsum (PG), a solid by-product of phosphoric acid production, contains radionuclides and trace metals in concentrations which may pose a potential hazard to human health and the environment. to investigate the possibility of bioaccumulation of radium and six heavy metals over time when aquatic organisms experience both trophic and environmental exposure to PG, we designed a laboratory experiment representing three levels of an aquatic food chain. During the 135 day experiment, a meiobenthic copepod species (Amphiascoides atopus) was cultured in the presence of PG. the copepods were subsequently fed to grass shrimp (Palaemonetes vulgaris and P. pugio) which were in turn fed to gulf killifish (Fundulus grandis); both the grass shrimp and the killifish also experienced an environmental PG exposure. Other than elevated radium levels in the experimental grass shrimp, the experiment demonstrated little effect of environmental or trophic exposure to PG on microinvertebrates, macroinvertebrates, or fishes that could be attributed to PG. in all cases where increased concentrations were indicated within the experimental group, roughly equivalent increases in metal concentrations also occurred in the control group.     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

Effects of of V,Cr single and combined stress on the growth and physiological characteristics of wheat seedling

采用水培法研究了V（Ⅴ）、Cr（Ⅵ）单一及复合胁迫对小麦幼苗生长和生理特性的影响.结果表明,无论单一或复合胁迫,随着V、Cr浓度的增加,小麦幼苗鲜重、株高、叶绿素含量均呈先上升后下降的趋势.当V≤5 mg.L-1、Cr≤10 mg.L-1,小麦的鲜重、株高、叶绿素含量均高于对照,当V〉5 mg.L-1、Cr〉10 mg.L-1,则分别比对照降低0.2%—46.8%、0.8%—40.7%和2.5%—76.9%.丙二醛含量随着V、Cr胁迫浓度的增加而增大,与对照相比,含量增加了7.5%—251.6%.在V、Cr单一胁迫下,随着金属浓度增加细胞膜透性增大,比对照增加17.8%—59.8%,根系活力则下降8.1%—53.0%;复合胁迫时细胞膜透性先下降后上升,但始终高于对照,比对照增加了0.6%—126.2%;根系活力呈先升高后下降的趋势,降低6.1%—97.3%.研究表明在低浓度范围,复合胁迫在一定程度上可以缓解单一金属对小麦的毒害,对小麦幼苗生长具有拮抗作用;在高浓度范围两种金属复合胁迫对小麦幼苗的损伤和毒害作用比单一金属伤害更为严重,表现为协同作用.单一胁迫中Cr对小麦幼苗的毒性比V大.     

Biosorption potential of Cr(VI) by Kocuria sp. ASB107, a radio-resistant bacterium isolated from Ramsar,Iran

Heavy metal pollution in soil and wastewater is a worldwide environmental issue in which microorganisms play a significant role for its removal. In the present study, biosorption of Cr(VI) by the live and dead cells of Kocuria sp. ASB107, a radio-resistant bacterium, was investigated. The effect of contact time, solution pH, initial hexavalent chromium concentration and adsorbent dose on biosorption efficiency was studied. Also, live cells were further immobilised on various matrices by different techniques and then were examined for tolerance to chromium biosorption. Experimental results indicated that the removal efficiency of chromium increased with decrease in pH, initial Cr(VI) concentration, and also increase in adsorbent dose and the contact time. The maximum removal efficiency of live and dead cells at acidic pH of 4–4.5, contact time of 24 hours, adsorbent dose 1.6?g/100?mL and initial chromium concentration 25?mg/L were 82.4% and 69.2%, respectively. The adsorption data was described well by Langmuir isotherm model. Among all immobilisation techniques tested, cross-linking showed the highest biosorption of Cr(VI). Results indicated that live cells of Kocuria sp. ASB107 were better than dead ones.     

沼渣协同硫酸亚铁修复Cr(Ⅵ)污染土壤

通过稳定化实验、连续提取实验及植物毒性实验,研究了沼渣对硫酸亚铁稳定化Cr （Ⅵ）污染土壤的促进效果与机制.结果表明,沼渣协同硫酸亚铁对土壤中Cr （VI）有良好的稳定化效果.最佳的修复条件为：n（Fe）/n（Cr）=3∶1,含水率为35%,沼渣投加量为4.5%,反应时间为12 d,此时Cr （VI）稳定化效率为99.85%,残余六价铬含量为1.49 mg·kg^-1,满足《土壤环境质量建设用地土壤污染风险管控标准》（GB 36600—2018）第二类用地筛选值5.7 mg·kg^-1的限值要求.由连续提取实验结果可知,沼渣+硫酸亚铁稳定化处理后酸溶态铬含量显著降低,而可还原态、可氧化态和残渣态铬含量明显增加.风险分析进一步表明,沼渣+硫酸亚铁稳定化处理后铬的风险等级由非常高风险降至低风险.植物毒性分析可知,沼渣+硫酸亚铁稳定化处理植物毒性显著降低.微生物多样性和群落结构分析可知,沼渣+硫酸亚铁稳定化处理后土壤中细菌群落的丰度和多样性均明显增加.